Thermodynamic equilibrium temperature scale

Approximately every twenty years, the international temperature scale is updated to incorporate the most recent measurements of the equilibrium thermodynamic temperature of the fixed points, to revise the interpolation equations, or to change the specifications of the interpolating measuring devices. The latest of these scales is the international temperature scale of 1990 (ITS-90). It supersedes the earlier international practical temperature scale of 1968 (IPTS-68), along with an interim scale (EPT-76). These temperature scales replaced earlier versions (ITS-48 and ITS-27). 

Note that Eq. (6) includes thermodynamic equilibrium (v° = 0) as a special case. However, usually the steady-state condition refers to a stationary nonequilibrium state, with nonzero net flux and positive entropy production. We emphasize the distinction between network stoichiometry and reaction kinetics that is implicit in Eqs. (5) and (6). While kinetic rate functions and the associated parameter values are often not accessible, the stoichiometric matrix is usually (and excluding evolutionary time scales) an invariant property of metabolic reaction networks, that is, its entries are independent of temperature, pH values, and other physiological conditions. 

A fluid composed of a single species is described by five fields the three components of the velocity, the mass density, and the temperature. This is a drastic reduction of the full description in terms of all the degrees of freedom of the particles. This reduction is possible by assuming the local thermodynamic equilibrium according to which the particles of each fluid element have a Maxwell-Boltzmann velocity distribution with local temperature, velocity, and density. This local equilibrium is reached on time scales longer than the intercollisional time. On shorter time scales, the degrees of freedom other than the five fields manifest themselves and the reduction is no longer possible. 

The KTTS depends upon an absolute zero and one fixed point through which a straight line is projected. Because they are not ideally linear, practicable interpolation thermometers require additional fixed points to describe their individual characteristics. Thus a suitable number of fixed points, ie, temperatures at which pure substances in nature can exist in two- or three-phase equilibrium, together with specification of an interpolation instrument and appropriate algorithms, define a temperature scale. The temperature values of the fixed points are assigned values based on adjustments of data obtained by thermodynamic measurements such as gas thermometry. 

When a hot body and a cold body are brought into physical contact, they lend to achieve the same warmth after a long lime. These two bodies are then said to be at thermal equilibrium with each other. The zeroth law of thermodynamics (R.H. Fowler) states that two bodies individually at equilibrium with a third are at equilibrium with each other. This led lo the comparison of the states of thermal equilibrium of two bodies in lei ms ol a third body called a thermometer. The temperature scale is a measure of state or thermal equilibrium, and tw-o systems at thermal equilibrium must have the same temperature. 

TEMPERATURE SCALES AND STANDARDS. That property of systems which determines whether they are in thermodynamic equilibrium. Two systems are in equilibrium when their temperatures (measured on die same temperature scale) are equal, The existence of the property defined as temperature is a consequence of the zeroth law of thermodynamics. The zerodi law of thermodynamics leads to the conclusion that in the case of all systems there exist functions of their independent properties j , such dial at equilibrium... 

The idea of a thermodynamic temperature scale was first proposed in 1854 by the Scottish physicist William Thomson, Lord Kelvin [iv]. He realized that temperature could be defined independently of the physical properties of any specific substance. Thus, for a substance at thermal equilibrium (which can always be modeled as a system of harmonic oscillators) the thermodynamic temperature could be defined as the average energy per harmonic oscillator divided by the Boltzmann constant. Today, the unit of thermodynamic temperature is called kelvin (K), and is defined as the fraction 1/273.16 of the thermodynamic temperature of the triple point of water. 

The zeroth law of thermodynamics involves some simple definition of thermodynamic equilibrium. Thermodynamic equilibrium leads to the large-scale definition of temperature, as opposed to the small-scale definition related to the kinetic energy of the molecules. The first law of thermodynamics relates the various forms of kinetic and potential energy in a system to the work which a system can perform and to the transfer of heat. This law is sometimes taken as the definition of internal energy, and introduces an additional state variable, enthalpy. 

Two systems in thermal contact eventually arrive at a state of thermal equilibrium. Temperature, as a universal function of the state and the internal energy, uniquely defines the thermal equilibrium. If system 1 is in equilibrium with system 2, and if system 2 is in equilibrium with system 3, then system 1 is in equilibrium with system 3. This is called the zeroth law of thermodynamics and implies the construction of a universal temperature scale (stated first by Joseph Black in the eighteenth century, and named much later by Guggenheim). If a system is in thermal equilibrium, it is assumed that the energy is distributed uniquely over the volume. Once the energy of the system increases, the temperature of the system also increases (dU/dT> 0). 

A fundamental attribute of temperature is that for any body in a state of equilibrium the temperature may be expressed by a number on a temperature scale, defined without particular reference to that body. The applicability of a universal temperature scale to all physical bodies at equilibrium is a consequence of an empirical law (sometimes called the zeroth law of thermodynamics ), which states that if a body is in thermal equilibrium separately with each of two other bodies these two will be also in thermal equilibrium with each other. 

The influence of the applied reaction conditions (temperatme, residence time, concentrations of reactants and products) on the product spectra obtained from pyrolysis of different plastic wastes could be estimated under the hypothesis of thermodynamic equilibrium, as shown by Westerhout et al. [43]. They evaluated the maximum achievable yield of valuable products during the pyrolysis of PE and PP, with the validation of experiments carried out under conditions of controlled temperatme and residence time. In large-scale reactors the residence time and temperature control are difficult and certainly... 

Ideal-gas tables of thermodynamic properties derived from statistical mechanics are based on the thermodynamic temperatures (as well as on the values of the physical constants used) and are hence independent of any practical temperature scale. The enthalpy of formation, Gibbs energy of formation, and logarithm of the equilibrium constant might depend on temperature-adjusted data. 

Blackbody radiation is achieved in an isothermal enclosure or cavity under thermodynamic equilibrium, as shown in Figure 7.4a. A uniform and isotropic radiation field is formed inside the enclosure. The total or spectral irradiation on any surface inside the enclosure is diffuse and identical to that of the blackbody emissive power. The spectral intensity is the same in all directions and is a function of X and T given by Planck s law. If there is an aperture with an area much smaller compared with that of the cavity (see Figure 7.4b), X the radiation field may be assumed unchanged and the outgoing radiation approximates that of blackbody emission. All radiation incident on the aperture is completely absorbed as a consequence of reflection within the enclosure. Blackbody cavities are used for measurements of radiant power and radiative properties, and for calibration of radiation thermometers (RTs) traceable to the International Temperature Scale of 1990 (ITS-90) [5]. 

Intensive signals behave in a nonadditive manner, as is true for pressure and temperature. When the size of a system is increased, the signal value remains constant and does not scale with system dimensions. Intensive signals can therefore be measured within small parts of a system - but only when it is at (local) thermodynamic equilibrium - and so miniaturization is limited only by resolution aspects and by mounting requirements. 

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